The reaction between Dy(NO3)3·6H2O, Zn(OAc)2·4H2O, salicylaldehyde and 2-amino-isobutyric acid, in MeOH in the presence of NEt3 under solvothermal conditions, led to the isolation of the triacontanuclear mixed-metal cluster [ZnII12DyIII18(OH)30(L)12(sal)6(OAc)6(NO3)3(H2O)6](NO3)3·12MeOH·5H2O (1·12MeOH·5H2O), which displays frequency- and temperature-dependent out-of-phase magnetic susceptibility signals.

Employment of H3L (= 2-(β-naphthalideneamino)-2-hydroxymethyl-1-propanol) in mixed-metal copper-lanthanide cluster chemistry has led to the isolation of four new enneanuclear heteronuclear isostructural [CuII7LnIII2] complexes. More specifically, the solvothermal reaction of Cu2(OAc)4·2H2O with H3L and the corresponding lanthanide nitrate salt in MeCN in the presence of a base, NEt3, yielded three complexes with the general formula [CuII7LnIII2(L)4(HL)2(OAc)4]·2MeCN (Ln: Gd, 1·2MeCN; Tb, 2·2MeCN; Dy, 3·2MeCN), while in addition the YIII analogue, [CuII7YIII2(L)4(HL)2(OAc)4]·2MeCN (4·2MeCN), was also synthesized in the same manner. The structure of the cluster describes two corner-sharing [Cu3Ln] cubane metallic units, each one further connected to one CuII ion. Dc magnetic susceptibility studies in the 5–300 K range for complexes 1–4 reveal the presence of both ferromagnetic and antiferromagnetic exchange interactions within the metallic clusters.

The use of pyridine-2-amidoxime (pyaoxH2) in Ni chemistry has provided access to a dodecanuclear complex and a hexadecanuclear Ni cluster, namely [Ni12(pyaox)6(pyaoxH)6(MeOH)2Cl2]Cl4·5MeOH (1·5MeOH) and [Ni16(pyaox)8(pyaoxH)8(MeOH)4](SO4)4·10H2O·26MeOH (2·10H2O·26MeOH). Complex 1·5MeOH was isolated by the reaction of NiCl2·6H2O, pyaoxH2 and NaOMe in a 1:1:2 molar ratio in MeOH in 60% yield. Treatment of NiSO4·6H2O with pyaoxH2 and NEt3 in a 1:1:2 molar ratio in MeOH afforded 2·10H2O·26MeOH in good yield (65%). The two compounds display a multi-decker configuration based on stacked Ni4 layers, {Ni4(pyaox)2(pyaoxH)2}2+x (x = 3, 1·5MeOH; x = 4, 2·10H2O·26MeOH); each deck consists of two square planar and two octahedral NiII centres. The number of decks observed in 1·5MeOH and 2·10H2O·26MeOH depends on the nature of the inorganic anion that is present in the reaction system, which provides elements of synthetic control towards new high nuclearity NiII species. 2·10H2O·26MeOH is the first structurally characterized complex of any metal displaying a quadruple-decker configuration, being also the highest nuclearity metal cluster bearing pyaoxH2 and the highest nuclearity NiII cluster with any type of 2-pyridyl oxime. Each cluster cation displays ferromagnetic exchange between the octahedral NiII ions resulting in a spin ground state of S = 6 for 1 and S = 8 for 2. Magnetothermal studies have been performed and discussed for both clusters.

Employment of H3L (= 2-(β-naphthalideneamino)-2-hydroxymethyl-1-propanol) in mixed-metal copper-lanthanide cluster chemistry has led to the isolation of four new enneanuclear heteronuclear isostructural [CuII7LnIII2] complexes. More specifically, the solvothermal reaction of Cu2(OAc)4·2H2O with H3L and the corresponding lanthanide nitrate salt in MeCN in the presence of a base, NEt3, yielded three complexes with the general formula [CuII7LnIII2(L)4(HL)2(OAc)4]·2MeCN (Ln: Gd, 1·2MeCN; Tb, 2·2MeCN; Dy, 3·2MeCN), while in addition the YIII analogue, [CuII7YIII2(L)4(HL)2(OAc)4]·2MeCN (4·2MeCN), was also synthesized in the same manner. The structure of the cluster describes two corner-sharing [Cu3Ln] cubane metallic units, each one further connected to one CuII ion. Dc magnetic susceptibility studies in the 5–300 K range for complexes 1–4 reveal the presence of both ferromagnetic and antiferromagnetic exchange interactions within the metallic clusters.

The reaction between Dy(NO3)3·6H2O, Zn(OAc)2·4H2O, salicylaldehyde and 2-amino-isobutyric acid, in MeOH in the presence of NEt3 under solvothermal conditions, led to the isolation of the triacontanuclear mixed-metal cluster [ZnII12DyIII18(OH)30(L)12(sal)6(OAc)6(NO3)3(H2O)6](NO3)3·12MeOH·5H2O (1·12MeOH·5H2O), which displays frequency- and temperature-dependent out-of-phase magnetic susceptibility signals.